CN111875625A - Glucose-citric acid-zinc complex and preparation method and application thereof - Google Patents
Glucose-citric acid-zinc complex and preparation method and application thereof Download PDFInfo
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- citric acid
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- DGBMEXACPOMWPN-VAXZQHAWSA-N [Zn].C(CC(O)(C(=O)O)CC(=O)O)(=O)O.O=C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO Chemical compound [Zn].C(CC(O)(C(=O)O)CC(=O)O)(=O)O.O=C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO DGBMEXACPOMWPN-VAXZQHAWSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 45
- 239000008103 glucose Substances 0.000 claims abstract description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 34
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- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 11
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/06—Zinc compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/04—Antibacterial agents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
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Abstract
The invention belongs to the fields of food science and biomedicine, and relates to a zinc complex, in particular to a glucose-citric acid-zinc complex and a preparation method and application thereof. The method comprises the following steps: dissolving glucose and trisodium citrate in deionized water, and uniformly stirring to obtain a solution I; reacting ZnCl2Slowly dropwise adding a hydrochloric acid solution into the solution I, adjusting the pH value, heating in a water bath to react for a certain time, and adding ethanol until white precipitate exists; and centrifuging the reaction system, washing the precipitate with ethanol, volatilizing the ethanol, dissolving in water, and freeze-drying to obtain white powder, namely PN-zinc. The PN-zinc complex prepared by the invention has good bacteriostatic activity on gram-positive bacteria and gram-negative bacteria, and the same effect is achievedThe bacteriostasis zone of the PN-zinc complex is ZnCl under the equal concentration21.5-2 times of the total amount of the active components, and the minimum use concentration is 0.75g/L, ZnZnCl under the condition of the concentration2The inhibition zone does not exist.
Description
Technical Field
The invention belongs to the fields of food science and biomedicine, and relates to a zinc complex, in particular to a glucose-citric acid-zinc complex and a preparation method and application thereof.
Background
At present, a plurality of serious problems in clinic are closely related to various bacterial infections, and the traditional antibacterial drugs have multi-drug resistance in clinical use, so that the further research of the traditional antibacterial drugs is limited. More and more scientists are trying to find new antibiotics to solve the increasingly serious resistance problem. Some heavy metal ions having a biocidal effect, such as silver, zinc and copper, are the subject of current research, and have been made into various inorganic metal antibacterial materials. Although most inorganic metal antibacterial materials are toxic, zinc is the most specific of them and is a dietary trace metal necessary for some physiological and biochemical functions of human body, and the zinc deficiency can produce a series of harmful effects on immune system. Zinc has antibacterial effect, and zinc chloride is effective in inhibiting the growth of almost all strains causing halitosis and periodontal disease, resulting in direct decrease of bacterial yield. Zinc ions inhibit the formation and growth of dental plaque and may be used in toothpaste and mouthwash in the future. A common treatment for damaged skin is the use of steroids, but such drugs often have a significant damaging effect on the immune system of the human body, and are therefore fatal to misdiagnosis of infection or misuse of steroids. The zinc-containing wound dressing is a common external dressing and can promote the healing of chronic and acute wounds. There is much evidence that zinc has an anti-infective effect in damaged skin and tissues with few side effects. In addition, zinc ions also have a protein precipitating effect, leading to tissue shrinkage, corrosion and chemical fixation. However, zinc chloride has certain toxicity and strong capability of penetrating tissues, and the ingestion of low-concentration zinc chloride can cause irritation to gastrointestinal mucosa, cause slight corrosion to pylorus, oropharynx or esophagus, and cause vomiting, abdominal pain and diarrhea. Ingestion of high concentrations of zinc chloride can lead to the formation of pyloric obstructive scarring. The study of various zinc complexes has attracted considerable attention in order to reduce the toxicity and irritation of free zinc ions. The development of chelated zinc is a potential therapeutic drug, which can inhibit the development of bacterial biofilms. Zinc can reduce clinical infection by weakening the activity of Streptococcus pyogenes, inducing intercellular adhesion of Staphylococcus epidermidis and Staphylococcus. Trisodium citrate is a commonly used multifunctional ligand for preparing complexes, has obvious biochemical activity, however, citrate is easy to combine with zinc ions to generate zinc citrate which is slightly soluble in water, and in order to prepare a water-soluble zinc citrate complex, glucose, trisodium citrate and zinc chloride are used as raw materials, and a novel zinc complex (PN-zinc) is synthesized through a simple reaction. The antibacterial activity of the PN-zinc complex against gram-positive bacteria (staphylococcus aureus) and gram-negative bacteria (escherichia coli), as well as acute toxicity, were determined. Research results show that the novel zinc complex has good antibacterial activity and can be applied to food packaging antibacterial materials and other biomedical fields.
Disclosure of Invention
In order to solve the technical problem that in the process of improving the zinc performance, citrate is easy to combine with zinc ions to generate zinc citrate which is slightly soluble in water, the invention provides a glucose-citric acid-zinc complex and a preparation method and application thereof.
The technical scheme of the invention is realized as follows:
a preparation method of a glucose-citric acid-zinc complex comprises the following steps:
(1) dissolving glucose and trisodium citrate in deionized water, and uniformly stirring to obtain a solution I;
(2) reacting ZnCl2Slowly dropwise adding a hydrochloric acid solution into the solution I obtained in the step (1), adjusting the pH value, heating in a water bath to react for a certain time, and adding ethanol until white precipitate exists;
(3) and (3) centrifuging the reaction system in the step (2), washing the precipitate with ethanol, volatilizing the ethanol, dissolving the ethanol in water, and freeze-drying to obtain white powder, namely the glucose-citric acid-zinc complex named PN-zinc.
The glucose, trisodium citrate and ZnCl2In a molar ratio of (1-6): 1: (0.8-1.2).
The concentration of the hydrochloric acid solution in the step (2) is 0.1 mol/L.
The pH value of the water bath heating reaction in the step (2) is 5.5-7.5, the temperature is 30-70 ℃, and the time is 12-48 h.
The alcohol content of the reaction system after the ethanol is added in the step (2) reaches 65-90% v/v.
The centrifugation condition in the step (3) is 4000rpm for 2 min.
The glucose-citric acid-zinc complex has the chemical structure as follows:
the glucose-citric acid-zinc complex is used for improving ZnCl2Application in bacteriostasis performance.
The glucose-citric acid-zinc complex is heated at 130 ℃ for 1h, blue solid fluorescence appears under a 365nm ultraviolet lamp, and the glucose-citric acid-zinc complex is used for a solid fluorescent material or for preparing an LED lamp.
The invention has the following beneficial effects:
1. the invention prepares the PN-zinc complex with good water solubility for the first time, and can be used for zinc supplement, blood sugar reduction and the like. The molecular weight of the prepared PN-zinc complex is larger than 1000Da, the PN-zinc complex can stably exist in an aqueous solution for more than 48 hours, and the PN-zinc complex can be stably maintained below 170 ℃.
2. The invention uses glucose, trisodium citrate and ZnCl2In the PN-zinc complex prepared by taking the raw material as the raw material, the ratio of alpha-stereoisomer to beta-H stereoisomer of glucose is 1:2.04, trisodium citrate is coordinated with zinc ion through carboxyl oxygen, glucose participates in coordination through forming hydrogen bond (comprising adsorbed small amount of crystal water and ethanol), wherein acid radical in trisodium citrate ligand forms the complex in a monodentate coordination mode.
3. The PN-zinc complex prepared by the invention has good bacteriostatic activity on gram-positive bacteria and gram-negative bacteria, and the bacteriostatic zone of the PN-zinc complex is ZnCl under the same concentration21.5-2 times of the total amount of the active components, and the minimum use concentration is 0.75g/L, ZnZnCl under the condition of the concentration2The inhibition zone does not exist. The zinc ions in the PN-zinc complex can adhere to the negatively charged bacterial cell wall through electrostatic interaction and combine with the proteins and nucleic acids of bacteria, thereby destroying the cell wall, causing cell distortion and losing vitality. The multidentate organic ligand and the central zinc ion form PN-z through coordination bond self-assemblyinc complex with the same concentration of ZnCl2In contrast, the PN-zinc has an unobvious bacteriostatic ring edge, which may be caused by the fact that the PN-zinc complex exerts bacteriostatic action in both molecular and zinc ion forms. When the molar concentration of zinc ions is the same, the inhibition zones of the PN-zinc complexes are all obviously greater than that of ZnCl2. PN-zinc and ZnCl2The MIC values of the complex for staphylococcus aureus are 650 mu g/mL and 900 mu g/mL (zinc ion concentration) respectively, and the MIC values for escherichia coli are 650 mu g/mL and 900 mu g/mL (zinc ion concentration) respectively, which shows that the bacteriostatic activity of the PN-zinc complex is higher than that of ZnCl2And the complex has no or very little toxicity to mice when the acute toxicity test proves that the complex has 1300mg/kg toxicity, and can be used as a potential food and drug antibacterial material.
4. The glucose-citric acid-zinc complex prepared by the invention is heated for 1h at 130 ℃, blue solid fluorescence appears under a 365nm ultraviolet lamp, and the glucose-citric acid-zinc complex can be used for solid fluorescent materials.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows HPLC charts of citric acid standard (A) and sample (B).
FIG. 2 shows a PN-zinc scanning electron micrograph (A) and an energy spectrum (B).
FIG. 3 is a chart of glucose, trisodium citrate and PN-zinc infrared spectra.
FIG. 4 is an XRD pattern for trisodium citrate and PN-zinc.
FIG. 5 is a thermogravimetric plot of glucose, trisodium citrate and PN-zinc.
FIG. 6 shows a 1H spectrum (A) and a 13C NMR spectrum (B) of glucose; 1H NMR spectrum (C), 13CNMR spectrum (D) of trisodium citrate dihydrate; PN-zinc 1H NMR spectrum (E), 13C NMR spectrum (F).
FIG. 7 shows GTC-Zn XPS survey (A) and the peak separation of Zn (B).
FIG. 8 shows PN-zinc (circled numbers) and ZnCl2Inhibition of Staphylococcus aureus (A) and Escherichia coli (B) (without circled numbers).
FIG. 9 shows [ Zn (H) ]2O)]2n[Zn(Hcit)2]nSchematic structural diagram of (1).
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Examples
Firstly, optimizing a PN-zinc synthesis process:
preliminary experiments found that the viscosity of the PN-zinc complex rapidly increases with increasing pH of the solution, resulting in difficulty in drying it. According to NMR and ICP measurements, the glucose content was very low and the zinc content was low when the pH of the solution was less than 5. When the solution pH is greater than 8, glucose is easily oxidized in water. Therefore, the pH ranges were 5.5, 6.5 and 7.5. In preliminary experiments for examining the amount of glucose added, it was found that ZnCl occurred when the amount of glucose added was 02Must not be greater than the moles of trisodium citrate, otherwise excess ZnCl2A large amount of white precipitate is produced because the citrate and zinc form slightly water-soluble zinc citrate, with a portion of the ZnCl2The hydrolysis produces zinc hydroxide. When the amount of glucose added is small, white precipitates also appear during the reaction, and in order to make the formation of a complex of glucose easier, the equilibrium of the reaction is shifted toward the product, so that an excess of glucose is added, and the ratio of glucose to trisodium citrate is set to 4: 1.
Table a results of orthogonal tests and analysis table
The zinc content is closely related to the antibacterial effect and is an important index, the higher the zinc content is, the better the antibacterial effect is, and therefore the zinc content is used as a main index for screening the synthesis process. Have studied ZnCl2The influence of the addition amount, the reaction temperature, the pH value and the reaction time on the synthesis of the PN-zinc complex, and the orthogonal experiment result of the PN-zinc synthesis process is shown in a table a.
As can be seen from the variance value of Table a, the factor affecting the zinc content in PN-zinc is A>B>C>D, i.e. ZnCl2Amount of addition>pH value of reaction>Reaction time>The temperature of the water bath and the optimal reaction conditions are A2B2C2D 1. As can be seen from Table b, only factor A is ZnCl2The addition amount has significant difference, and other factors have little influence. In view of binding yield, when ZnCl is used2When the amount of zinc citrate added is 2.2mmol, a small amount of zinc citrate and Zn (OH) will be precipitated from the solution due to the increase of the reaction time2Precipitation, resulting in a decrease in yield. When the reaction pH is lowered, the coordination ability of zinc ions is weakened, resulting in a slight decrease in zinc content and yield. The yield slightly increased with increasing reaction time, but the reaction time continued to increase and a small amount of white turbidity formed in the solution. With the increase of the reaction temperature, the zinc content in the PN-zinc complex is slightly increased, and the solubility of the product is not changed significantly. Thus, the best reaction route, combining reaction yield and solubility, is: the adding amount of zinc is 2.0mmol, the reaction pH is controlled at 6.5, and the mixture is heated in water bath at 50 ℃ for 24 h. The PN-zinc complex prepared according to the optimal reaction conditions is white powder and is easy to dissolve in water, the yield is about 20.59 percent, and the zinc content is about 18.02 percent.
Table b analysis of variance table
The result of single factor investigation of the PN-zinc complex synthesis process is greatly different from the result of the dioscorea opposita polysaccharide zinc (DPSZn). First, when the pH is higher than 6.0, the solubility of DPSZn after lyophilization is significantly reduced, whereas PN-zinc is lower in zinc content and PN-zinc complexes need to be synthesized at higher pH. The coordination capacity of the dioscorea opposita polysaccharide and glucose to zinc is different, and the dioscorea opposita polysaccharide has a complex polysaccharide spiral structure, so that zinc ions can enter cavities of polysaccharide molecules, further combination of the zinc ions and citrate radicals is prevented from forming salts, and a complex is easier to form. Glucose is simple in structure and can only be combined by means of hydrogen bonds or electrostatic action, so that the combination capability of hydroxyl in glucose needs to be improved under neutral or weakly alkaline conditions. The prepared PN-zinc complex has excellent solubility, and the solubility of the dioscorea opposita polysaccharide zinc (DPSZn) is closely related to the polysaccharide.
Detection of di, PN-zinc complex structure
1. The content of zinc ions in the PN-zinc complex measured by the ICP method and the content of glucose in the complex measured by the iodometry method are shown in Table 1.
TABLE 1 determination of Zinc and glucose content
The measurement data of the sodium citrate standard curve are shown in table 1, and the standard curve equation is that y is 1330.4x +28.741, and r is 0.9997. The sodium citrate is proved to have good linear relation within the range of 0.10-1.50 g/L.
TABLE 2 citric acid Standard Curve data
HPLC chromatograms of the standard substance and the sample are shown in FIG. 1, and the content of citric acid in the PN-zinc complex is measured to be 48.05%.
From the above results, it is concluded that the sample also contains a small amount of Na, Cl and crystal water, and the molar ratio of Zn to glucose to citric acid in the PN-zinc complex is about 27.6:3.7:25.0, i.e., the molar ratio of zinc to citrate is about 1:1, and the molar ratio of glucose to citrate is about 1: 6.8.
2. PN-zinc characterization result
Scanning electron microscope results: the surface appearance of the PN-zinc complex is shown in figure 2(A), is in a lamellar shape, is amplified by 5000 times, and can be obviously seen that the surface is flat, smooth and uniform, which shows that zinc is connected with trisodium citrate in an ionic form through a coordination bond. The results of the energy spectrum analysis showed that there was a significant zinc signal in the PN-zinc complex (fig. 2B), again demonstrating the presence of zinc.
Infrared spectrum analysis: referring to FIG. 3, we compare the IR spectra of PN-zinc complex, glucose and trisodium citrate dihydrate, with the major vibrational peak wavenumbers of the IR spectra shown in Table 3. PN-zinc at 3410cm-1A broad peak appears on the left and right, mainly corresponding to the stretching vibration of O-H, and the broad peak indicates that a large number of intermolecular hydrogen bonds exist in the complex. The concentration of glucose and trisodium citrate is 2960-2800 cm-1The multiple C-H stretching vibration peak in between almost disappears in PN-zinc. It is possible that after the complex formation, the C-H bond stretching vibration peak shifts to a high wavenumber and is masked by the O-H stretching vibration peak. It is suggested that trisodium citrate ligand may coordinate through carboxyl and zinc oxygen atoms, and that the binding of zinc changes the strength of C-H. Meanwhile, the O-C ═ O stretching vibration peak in trisodium citrate is 1590.5cm-1Moved to 1604.7cm-1Again, the carboxyl group is shown to participate in the coordination reaction. There is a report in the literature that when the difference between the asymmetric stretching vibration and the symmetric stretching vibration wave number in the carboxylate radical (Δ ν ═ ν)asCOO--νsCOO-) When the chelating rate is more than 200, the chelating is monodentate; when bidentate chelation is desired, Δ ν is typically less than 200cm-1. Two vibration peaks of carboxylate radical in PN-zinc are respectively 1604.72cm-1And 1394.52cm-1I.e. vasCOO-And vsCOO-Is 210.20cm-1This indicates that the zinc in the PN-zinc complex is coordinated to the carboxylate in trisodium citrate by monodentate chelation. At 915.0cm-1A new vibration absorption peak occurs, which is caused by bending vibration of hydroxyl groups in Zn — OH. Furthermore, the infrared spectroscopy confirmed that zinc chloride combines with glucose and trisodium citrate to form a novel PN-zinc complex.
TABLE 3 PN-zinc, glucose and trisodium citrate RedMain vibration peak and wave number (cm) of external spectrum-1)。
Annotating a stricting symmetry; ν as strolling asymmetric.
X-ray powder diffraction: on the X-ray powder diffraction pattern of PN-zinc (FIG. 4), no distinct peaks appear, but many distinct crystalline peaks can be seen with trisodium citrate. Indicating that PN-zinc is amorphous in nature, and zinc exists in the complex in the form of zinc ions. This is probably the reason why the zinc ion binds to trisodium citrate through a coordination bond, again demonstrating the formation of the complex.
Thermogravimetric analysis results: the TGA/DTG curve for PN-zinc, glucose, trisodium citrate dihydrate is shown in FIG. 5. Trisodium citrate dihydrate has four distinct weight loss platforms. The first mass mutation was around 170 ℃ with a mass loss of about 13.8%, which was similar to a water of crystallization content of 12.3%. Thus, the first mass jump is mainly due to the decomposition of the crystallization water. The second and third mass mutations are mainly around 310 ℃ and 480 ℃, which may be due to decomposition, carbonization of their chemical structures. The last mass mutation of trisodium citrate dihydrate occurs at 860-1000 ℃, which indicates that the sample is completely carbonized, and the total weight loss is about 70.70%. The glucose does not contain crystal water, the mass mutation occurs at about 200-400 ℃, and the total weight loss is about 88.41%. For PN-zinc, a first endothermic peak is observed at about 75 ℃, with a small amount of water or ethanol adsorbed being evaporated. A second significant mass change occurs at around 250 c and may be the result of loss of intramolecular coordinated water and breakdown of the molecular structure. The weight of the PN-zinc complex decreases with increasing temperature. Then, a mass continuous weight loss of the PN-zinc complex occurs between 400 and 430 ℃, and the total weight loss of the PN-zinc complex is 66.42 percent when the temperature reaches 1000 ℃, which is in cooperation with the PN-zinc complex, zinc and oxygen atoms[28]The breakdown of the bond is relevant. Comparison of the thermogravimetric curves of PN-zinc, glucose and trisodium citrate dihydrate further confirms that PN-zinc forms a new complex.
Nuclear magnetic analysis results: the NMR spectra of glucose, trisodium citrate dihydrate and PN-zinc are shown in FIG. 6, and the solvent is heavy water. It can be seen that glucose has two stereoisomers, mainly in the form of hexose pyrans, present in aqueous solution, which are caused by the different steric positions of the hydroxyl groups on C1, this isomer being called anomer. Glucose is usually anomeric in water within hours. In stereoisomeric equilibrium in water, the ratio of alpha-to beta-D-glucose is 36: 64. However, in the 1H nuclear magnetic resonance diagram of PN-zinc, the ratio of alpha-H to beta-H is 1:2.04, which shows that the complex has certain influence on the stereoisomerism of glucose. In table 4, the nmr shifts for trisodium citrate dihydrate without coordination are H (fig. 5-6C): 2.59(H (a); J ═ 12Hz), 2.44(H (b); J ═ 12Hz), respectively; c (FIGS. 5-6D) (ppm)180.26(C1), 177.60(C2), 73.45(C3), 44.06 (C4). The nuclear magnetic resonance shifts of trisodium citrate in the PN-zinc complex are respectively H (figures 5-6E): 2.655(H (A); J ═ 18Hz), 2.49(H (B); J ═ 18 Hz); c (FIGS. 5-6F) (ppm)181.29 (C1), 178.45(C2), 74.97(C3), 44.06 (C4). These shift values change confirming that the PN-zinc complex is due to the coordination of the carboxyl group in trisodium citrate. Although the 1H and 13C NMR spectra before and after glucose coordination are not obviously changed, the three-dimensional structure property is changed, and the fact that glucose possibly participates in the formation of a complex through hydrogen bonds is shown. NMR results confirmed that trisodium citrate coordinates to zinc ions through the carboxyl oxygen and glucose participates in the coordination by forming hydrogen bonds (including adsorbed small amounts of crystalline water and ethanol). From the ratio of the peak area of hydroxyl hydrogen on glucose C1 to trisodium citrate, the ratio of glucose to trisodium citrate is estimated to be about 1:6, which is close to the result of the content measurement, 1: 6.8.
TABLE 4 chemical shift values of 1H and 13C NMR spectra of glucose, trisodium citrate dihydrate and PN-zinc
XPS analysis of PN-zinc complexes: from the XPS results (FIG. 7) of PN-zinc, it is found that the constituent elements of the complex are Zn and Na. O, C, Zn exists in two ways in the complex. Through hydrogen bond participation in the complex, acid radicals in trisodium citrate ligand form the complex in a monodentate coordination mode. The structure of the PN-zinc complex is presumed as follows:
wherein, O' may be connected with other citrate or connected with aldehyde group in glucose, thereby forming a complex grid structure as shown in FIG. 9.
Examples of the effects of the invention
1. The result of the PN-zinc antibacterial performance is as follows: gram-positive bacteria and gram-negative bacteria are infectious pathogenic bacteria caused by various diseases such as wound, cancer and the like, have certain adaptability and adjustability, and generate drug resistance to various drugs[32]The method is important for effectively inhibiting the growth of bacteria and continuously improving the antibacterial material. Therefore, we investigated the antibacterial activity of PN-zinc complexes against Staphylococcus aureus (gram-positive) and Escherichia coli (gram-negative) using agar plate punch diffusion. And placing the PN-zinc sample in an agar plate hole for a screening test, and analyzing the size of the inhibition zone. The PN-zinc complex shows good bacteriostatic activity on both gram-positive bacteria and gram-negative bacteria (see Table 5 and figure 8), and the inhibition band gradually increases with the increase of the concentration of PN-zinc.
TABLE 5 inhibition zone diameter of PN-zinc against Staphylococcus aureus and Escherichia coli
Note:The data are displayed as mean±SD from three independentexperiments
The reason why the PN-zinc complex produces the antibacterial effect is closely related to zinc ions. The zinc ions in the PN-zinc complex can adhere to the negatively charged bacterial cell wall through electrostatic interaction and combine with the proteins and nucleic acids of bacteria, thereby destroying the cell wall, causing cell distortion and losing vitality. A multidentate organic ligand and central zinc ions form a PN-zinc complex through coordination bond self-assembly,with the same concentration of ZnCl2In contrast, the PN-zinc has an unobvious bacteriostatic ring edge, which may be caused by the fact that the PN-zinc complex exerts bacteriostatic action in both molecular and zinc ion forms. When the molar concentration of zinc ions is the same, the inhibition zones of the PN-zinc complexes are all obviously greater than that of ZnCl2. PN-zinc and ZnCl2The MIC values of the complex for staphylococcus aureus are 650 mu g/mL and 900 mu g/mL (zinc ion concentration) respectively, and the MIC values for escherichia coli are 650 mu g/mL and 900 mu g/mL (zinc ion concentration) respectively, which shows that the bacteriostatic activity of the PN-zinc complex is higher than that of ZnCl2。
2. Acute toxicity test: the PN-zinc complex is respectively given with different doses, and the respiratory distress, the emaciation, the posture, the behavior, the autonomy and the toxicity of the experimental mouse low dose group have no obvious change. In the mice with the 1000mg/kg Body Weight (BW) dose group, the mice have the phenomena of reduced activity, lethargy, poor appetite and the like within 24 hours, and the two groups of mice recover to be normal after 48 hours. No animal death was observed by oral administration of all doses during the 14 day observation period, indicating that the PN-zinc complex was not acutely toxic. The PN-zinc complex has low toxicity and can be used as a potential food and drug antibacterial material.
3. Discussion:
(1) the glucose-citric acid-zinc complex PN-zinc is designed and synthesized, and reaction parameters are optimized through an orthogonal test. The chemical components of the complex are measured, the structure is characterized, and the molecular structure of the complex is presumed. The glucose-citric acid-zinc complex is heated at 130 ℃ for 1h, blue solid fluorescence can be observed under a 365nm ultraviolet lamp, and the glucose-citric acid-zinc complex can be used for manufacturing LED lamps or solid fluorescent materials.
(2) The acute toxicity of the PN-zinc complex is detected, and the PN-zinc complex is safe to Kunming mice at 1300 mg/kg. The antibacterial performance of PN-zinc on gram-positive bacteria (staphylococcus aureus) and gram-negative bacteria (escherichia coli) is detected, and ZnCl with the same concentration is found2Compared with the prior art, the antibacterial agent has lower toxicity and more excellent antibacterial effect, and is expected to be applied to the fields of controlled release of drugs, antibacterial materials and other biomedicine.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. A preparation method of a glucose-citric acid-zinc complex is characterized by comprising the following steps:
(1) dissolving glucose and trisodium citrate in deionized water, and uniformly stirring to obtain a solution I;
(2) reacting ZnCl2Slowly dropwise adding a hydrochloric acid solution into the solution I obtained in the step (1), adjusting the pH value, heating in a water bath to react for a certain time, and adding ethanol until white precipitate exists;
(3) and (3) centrifuging the reaction system in the step (2), washing the precipitate with ethanol, volatilizing the ethanol, dissolving the ethanol in water, and freeze-drying to obtain white powder, namely the glucose-citric acid-zinc complex named PN-zinc.
2. The method for preparing a glucose-citric acid-zinc complex according to claim 1, wherein: the glucose, trisodium citrate and ZnCl2In a molar ratio of (1-6): 1: (0.8-1.2).
3. The method for preparing a glucose-citric acid-zinc complex according to claim 1, wherein: the concentration of the hydrochloric acid solution in the step (2) is 0.1 mol/L.
4. The method for preparing a glucose-citric acid-zinc complex according to claim 1, wherein: the pH value of the water bath heating reaction in the step (2) is 5.5-7.5, the temperature is 30-70 ℃, and the time is 12-48 h.
5. The method for preparing a glucose-citric acid-zinc complex according to claim 1, wherein: the alcohol content of the reaction system after the ethanol is added in the step (2) reaches 65-90% v/v.
6. The method for preparing a glucose-citric acid-zinc complex according to claim 1, wherein: the centrifugation condition in the step (3) is 4000rpm for 2 min.
7. The glucose-citric acid-zinc complex prepared by the method of any one of claims 1 to 6, wherein the chemical structure of the glucose-citric acid-zinc complex is:
。
8. the glucose-citric acid-zinc complex of claim 7 in increasing ZnCl2Application in bacteriostasis performance.
9. The glucose-citric acid-zinc complex of claim 7, which is heated at 130 ℃ for 1h, and emits blue solid fluorescence under 365nm ultraviolet lamp, and is used for solid fluorescent materials.
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